CN110078678A - The diisocyanate and its preparation method and application of fluorine-containing carbon branch - Google Patents
The diisocyanate and its preparation method and application of fluorine-containing carbon branch Download PDFInfo
- Publication number
- CN110078678A CN110078678A CN201910342375.9A CN201910342375A CN110078678A CN 110078678 A CN110078678 A CN 110078678A CN 201910342375 A CN201910342375 A CN 201910342375A CN 110078678 A CN110078678 A CN 110078678A
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- CN
- China
- Prior art keywords
- diisocyanate
- preparation
- fluorine
- containing carbon
- carbon branch
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/773—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
Abstract
The present invention provides a kind of diisocyanate and its preparation method and application of fluorine-containing carbon branch, the preparation method passes through nucleophilic addition, it is reacted to obtain the diisocyanate of fluorine-containing carbon branch using isocyanate trimer and perfluoroalkyl ethyl alcohol, which is applied in polyurethane water-proof paint, adhesive, novel spandex fibre and leather finish；The diisocyanate contains the hydrophobic oleophobic group of perfluoroalkyl and the reactive group of two functional group's isocyanates, it can be reacted with polyether polyol or polyester polyol, it is colorless and transparent to generate the polyurethane resin of the fluorocarbon group with hydrophobic oleophobic performance, it is good with the compatibility of various types of resins；The preparation process of the diisocyanate is easy to operate, and the side reaction in reaction process is few, high reliablity, safety and environmental protection, has preferable industrial application value.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to a kind of diisocyanate and its system of fluorine-containing carbon branch
Preparation Method and application.
Background technique
Polyurethane is a kind of high molecular synthetic resin with excellent physical mechanical property and chemical-resistant stability, extensively
Applied to national product every field.As the primary raw material of synthesis of polyurethane, diisocyanate must can not as dihydric alcohol
It is few.Conventional diisocyanate includes aliphatic diisocyanate and aromatic diisocyanate, other than isocyanate groups,
It is all hydrocarbon branch or phenyl ring.Synthesizing, there is the diisocyanate of fluorocarbon chain to have for the polyurethane resin for synthesizing high fluorinated volume
There is great significance.
Fluorocarbon material is used widely in weaving, papermaking and paint field, especially life of the non-stick pan coating to people
Work brings great convenience.These self-cleaning surfaces have good hydro-oleophobicity and stronger contamination resistance, i.e. table
The water droplet that face pollutant such as dust etc. can be tumbled is taken away without leaving any trace.Automatic cleaning coating has water-saving, energy saving
With the advantages such as environmental protection, gets more and more extensive concerning of people, be one of the hotspots in the research of material science.
Past when synthesizing fluorochemical urethane, only reacts perfluoroalkyl second in the grafting to of base polyurethane prepolymer for use as
Base alcohol also introduces fluorocarbon group as diol component using fluorine-containing polyalcohol so that the fluorinated volume of polyurethane resin is lower,
But the perfluoroalkyl on main chain does not have good hydrophobic oleophobic characteristic.
Summary of the invention
Aiming at the shortcomings in the prior art, primary and foremost purpose of the invention is to provide a kind of diisocyanate of fluorine-containing carbon branch
Preparation method.
A second object of the present invention is to provide the diisocyanate of above-mentioned fluorine-containing carbon branch.
Third object of the present invention is to provide the purposes of the diisocyanate of above-mentioned fluorine-containing carbon branch.
In order to achieve the above objectives, solution of the invention is:
A kind of preparation method of the diisocyanate of fluorine-containing carbon branch comprising following steps:
(1), organic solvent is added in isocyanate trimer reduces viscosity, continues after adding perfluoroalkyl ethyl alcohol
20 ± 1min is stirred, the mixture of the uniform dissolution of isocyanic acid tripolymer and perfluoroalkyl ethyl alcohol in organic solvent is obtained；
(2), organo metallic oxide class catalyst is added in mixture, lasting to stir while being warming up to 70-80 DEG C, guarantor
20 ± 1min of reaction is held, for the content of hydroxyl lower than after 0.1%, cooling obtains dissolving in organic solvent fluorine-containing in measurement system
The diisocyanate of carbon branch.
Preferably, the molar ratio of isocyanate trimer and perfluoroalkyl ethyl alcohol is 1:1.
Preferably, the molal quantity of organo metallic oxide class catalyst is the 0.2% of the molal quantity of isocyanate trimer.
Preferably, cyanate tripolymer is selected from toluene diisocyanate trimer, hexamethylene diisocyanate trimer
One or more of with 3- isocyanates methylene -3,5,5- trimethylcyclohexylisocyanate tripolymer.
Preferably, perfluoroalkyl ethyl alcohol is selected from one or more of perfluorobutylethyl alcohol and perfluoro hexyl ethyl alcohol.
Preferably, organo metallic oxide class catalyst is selected from dibutyl tin dilaurate and two (dodecyl sulphur) dibutyl
One or more of tin.
Preferably, organic solvent is selected from one or more of acetone and n,N-Dimethylformamide.
The diisocyanate of fluorine-containing carbon branch is obtained by above-mentioned preparation method.
A kind of diisocyanate of above-mentioned fluorine-containing carbon branch is in polyurethane water-proof paint, adhesive, novel spandex fibre
With the application in leather finish.
By adopting the above scheme, the beneficial effects of the present invention are:
The first, the present invention by nucleophilic addition preparation purity 99% or more fluorine-containing carbon branch diisocyanate
Ester, the diisocyanate contain the hydrophobic oleophobic group of perfluoroalkyl and the reactive group of two functional group's isocyanates, Neng Gouhe
Polyether polyol or polyester polyol reaction, to generate the polyurethane resin with the fluorocarbon group of hydrophobic oleophobic performance, nothing
Color is transparent, good with the compatibility of various types of resins.
The second, the preparation process of the diisocyanate of fluorine-containing carbon branch of the invention is easy to operate, the pair in reaction process
Reaction is few, high reliablity, safety and environmental protection, has preferable industrial application value.
Detailed description of the invention
Fig. 1 is infrared spectrum (the abscissa Wavenumber: wave of the diisocyanate of the fluorine-containing carbon branch of the present embodiment
Number, ordinate Transmittance: light transmittance).
Specific embodiment
The present invention provides a kind of diisocyanate and its preparation method and application of fluorine-containing carbon branch.
<preparation method of the diisocyanate of fluorine-containing carbon branch>
The preparation method of the diisocyanate of fluorine-containing carbon branch of the invention includes the following steps:
(1), first the four-hole boiling flask with stirring and reflux condenser is put into the large beaker of mixture of ice and water, is passed through lazy
Property gas or nitrogen, start simultaneously at stirring, sequentially add isocyanate trimer and organic solvent, be subsequently added into perfluoroalkyl second
Base alcohol (its reaction equation is as follows), after persistently 20 ± 1min of stirring is uniform, holding is passed through inert gas or nitrogen, obtains isocyanide
The mixture of the dissolution of sour tripolymer and perfluoroalkyl ethyl alcohol in organic solvent；
(2), after removing the beaker equipped with mixture of ice and water, organo metallic oxide class is continuously added in said mixture
Catalyst, persistently stirs and heats four-hole boiling flask and be warming up to 70-80 DEG C, keeps 20 ± 1min of reaction, hydroxyl in measurement system (-
OH it after content) is lower than 0.1%, is down to room temperature and stops being passed through inert gas or nitrogen, obtain dissolving in organic solvent
The diisocyanate of fluorine-containing carbon branch.
Wherein, above-mentioned reaction equation: R '-OH+R-NCO → R-NH-CO-O-R '.
In short, isocyanate trimer is with isocyanurate ring trifunctional oligomer, vapour pressure is high, volatility
It is low, it is not easy to evaporate into environment in use to cause harm to the human body, by hydroxyl on perfluoroalkyl ethyl alcohol and different
One-NCO group reaction in cyanate tripolymer introduces fluorocarbon chain, so that the diisocyanate generated has the function of fluorocarbon chain
Property, therefore the vapour pressure of the diisocyanate of fluorine-containing carbon branch of the invention is higher, volatility is low, small toxicity, introduces fluorocarbon radical
Corresponding polyurethane resin is made to have the characteristics that hydrophobic oleophobic is easy to clean after group.
Specific, the molar ratio of isocyanate trimer and perfluoroalkyl ethyl alcohol is 1:1.
The molal quantity of organo metallic oxide class catalyst is the 0.2% of the molal quantity of isocyanate trimer.
Cyanate tripolymer is selected from toluene di-isocyanate(TDI) (TDI) tripolymer, hexamethylene diisocyanate (HDI) trimerization
One or more of body and 3- isocyanates methylene -3,5,5- trimethylcyclohexylisocyanate (IPDI) tripolymer.
Perfluoroalkyl ethyl alcohol is selected from perfluorobutylethyl alcohol (TEOH-4) and perfluoro hexyl ethyl alcohol (TEOH-6)
More than one.
Organo metallic oxide class catalyst is selected from dibutyl tin dilaurate and two (dodecyl sulphur) dibutyl tins
More than one.
The purpose of organo metallic oxide class catalyst is: reaction can be accelerated to carry out, shorten the time of reaction.
Organic solvent is selected from one or more of acetone (DMK) and N,N-dimethylformamide (DMF).
In order to make fluorine-containing carbon branch diisocyanate viscosity to 2000 centipoises or so, a small amount of inertia, which can be added, to be had
Solvent.
<diisocyanate of fluorine-containing carbon branch>
The diisocyanate of fluorine-containing carbon branch of the invention is obtained by above-mentioned preparation method.
Fluorine-containing carbon branch diisocyanate can be aliphatic diisocyanate and be also possible to aromatic diisocyanate.
<application of the diisocyanate of fluorine-containing carbon branch>
The diisocyanate of fluorine-containing carbon branch of the invention can be fine in polyurethane water-proof paint, adhesive, novel spandex
It is applied in the fields such as peacekeeping leather finish.
The present invention is further illustrated with reference to embodiments.
Embodiment:
The preparation method of the diisocyanate of the fluorine-containing carbon branch of the present embodiment includes the following steps:
(1), first the four-hole boiling flask with stirring and reflux condenser is put into the large beaker of mixture of ice and water, is added
504g hexamethylene diisocyanate (HDI) tripolymer, is passed through nitrogen, starts simultaneously at stirring, and it is viscous to reduce that 30g acetone is added
Degree adds 364g perfluoro hexyl ethyl alcohol (TEOH-6), keeps obtaining hexamethylene diisocyanate trimerization after stirring 20min
The mixture of the uniform dissolution of body and perfluoro hexyl ethyl alcohol in acetone；；
(2), the beaker for removing mixture of ice and water continuously adds 1.26g dibutyl tin dilaurate in said mixture and (makees
For catalyst), continuous heating four-hole boiling flask is warming up to 70 DEG C, keeps reaction 20min, the content of hydroxyl (- OH) in measurement system
After 0.1%, it is down to room temperature and stops being passed through nitrogen, obtain dissolving the diisocyanate of fluorine-containing carbon branch in acetone,
And infrared test is carried out, as shown in Figure 1.
As shown in Figure 1, in 2273cm-1The asymmetric stretching vibration peak for locating appearance-N=C=O, in 1705cm-1Place occurs
The stretching vibration absworption peak of-C=O in carbamate, and in 1540cm-1There is the absorption of the amide II in polyurethane in place
Peak, in 3336cm-1Place is the N-H stretching vibration peak in carbamate, in 1400-1000cm-1Place is fluorine carbon key characteristic absorption
Peak, this just proves to contain perfluoro hexyl ethyl on isocyanates ring.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (9)
1. a kind of preparation method of the diisocyanate of fluorine-containing carbon branch, it is characterised in that: it includes the following steps:
(1), organic solvent is added in isocyanate trimer reduces viscosity, add stirring 20 after perfluoroalkyl ethyl alcohol ±
1min obtains the mixture of isocyanic acid tripolymer and perfluoroalkyl ethyl alcohol dissolved in organic solvent；
(2), organo metallic oxide class catalyst is added in the mixture, stirring is warming up to 70-80 DEG C simultaneously, keeps instead
20 ± 1min is answered, after measuring the content of hydroxyl in the system lower than 0.1%, cooling obtains dissolving in organic solvent fluorine-containing
The diisocyanate of carbon branch.
2. preparation method according to claim 1, it is characterised in that: the isocyanate trimer and the perfluoroalkyl
The molar ratio of ethyl alcohol is 1:1.
3. preparation method according to claim 1, it is characterised in that: mole of the organo metallic oxide class catalyst
Number is the 0.2% of the molal quantity of the isocyanate trimer.
4. preparation method according to claim 1, it is characterised in that: the isocyanate trimer is selected from toluene diisocyanate
Acid esters tripolymer, hexamethylene diisocyanate trimer and 3- isocyanates methylene -3,5,5- trimethylcyclohexyl are different
One or more of cyanate tripolymer.
5. preparation method according to claim 1, it is characterised in that: the perfluoroalkyl ethyl alcohol is selected from perfluoro butyl second
One or more of pure and mild perfluoro hexyl ethyl alcohol of base.
6. preparation method according to claim 1, it is characterised in that: the organo metallic oxide class catalyst is selected from two
One or more of two fourth tin of lauric acid and two (dodecyl sulphur) dibutyl tins.
7. preparation method according to claim 1, it is characterised in that: the organic solvent is selected from acetone and N, N- dimethyl
One or more of formamide.
8. a kind of diisocyanate of fluorine-containing carbon branch, it is characterised in that: it is obtained by above-mentioned preparation method.
9. a kind of diisocyanate of fluorine-containing carbon branch as claimed in claim 8 is in polyurethane water-proof paint, adhesive, novel
Application in spandex fibre and leather finish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910342375.9A CN110078678A (en) | 2019-04-26 | 2019-04-26 | The diisocyanate and its preparation method and application of fluorine-containing carbon branch |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910342375.9A CN110078678A (en) | 2019-04-26 | 2019-04-26 | The diisocyanate and its preparation method and application of fluorine-containing carbon branch |
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| CN110078678A true CN110078678A (en) | 2019-08-02 |
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| CN201910342375.9A Pending CN110078678A (en) | 2019-04-26 | 2019-04-26 | The diisocyanate and its preparation method and application of fluorine-containing carbon branch |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032017A (en) * | 2021-11-21 | 2022-02-11 | 北京理工大学 | Modified branched fluorinated polyurethane-based polyurethane wire enamel composition with high breakdown voltage and long service life and preparation method thereof |
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|---|---|---|---|---|
| CN1675176A (en) * | 2002-08-06 | 2005-09-28 | 大金工业株式会社 | Fluorinated urethane compounds and compositions containing the same |
| CN103980215A (en) * | 2014-05-23 | 2014-08-13 | 中国科学院长春应用化学研究所 | Waterborne polyurethane acrylate oligomer, preparation method thereof and waterborne ultraviolet curing coating |
| CN107778450A (en) * | 2017-11-10 | 2018-03-09 | 湖南辰砾新材料有限公司 | A kind of fluorine richness low free toluene diisocyanate polyurethane curing agent and preparation method thereof |
-
2019
- 2019-04-26 CN CN201910342375.9A patent/CN110078678A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675176A (en) * | 2002-08-06 | 2005-09-28 | 大金工业株式会社 | Fluorinated urethane compounds and compositions containing the same |
| CN103980215A (en) * | 2014-05-23 | 2014-08-13 | 中国科学院长春应用化学研究所 | Waterborne polyurethane acrylate oligomer, preparation method thereof and waterborne ultraviolet curing coating |
| CN107778450A (en) * | 2017-11-10 | 2018-03-09 | 湖南辰砾新材料有限公司 | A kind of fluorine richness low free toluene diisocyanate polyurethane curing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIATING WEN，等: "Synthesis and characterization of a novel fluorinated waterborne polyurethane", 《PROGRESS IN ORGANIC COATINGS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032017A (en) * | 2021-11-21 | 2022-02-11 | 北京理工大学 | Modified branched fluorinated polyurethane-based polyurethane wire enamel composition with high breakdown voltage and long service life and preparation method thereof |
| CN114032017B (en) * | 2021-11-21 | 2022-07-05 | 北京理工大学 | Modified branched fluorinated polyurethane-based polyurethane wire enamel composition with high breakdown voltage and long service life and preparation method thereof |
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Application publication date: 20190802 |